While presenting Aniston with one of the night's many awards, Witherspoon recalled how excited she was to play Aniston's sister on Friends back in 1999. The Oscar winner admitted she was, like most of the world, "obsessed" with the hit sitcom. She had just had her first baby, so "I would not stop watching Friends. They were my friends and there was no taking me away from my friends."

But then Witherspoon showed up for work. "In all my enthusiasm I completely forgot something very crucial—that I had never been on television ever before in my entire life and I never really had been in front of a live audience before ever in my entire life," she said to laughs in the packed ballroom at the Four Seasons Hotel in Beverly Hills. "I panicked. I totally froze. It became immediately clear to me that I had no idea what I was doing and I was completely out of my league."

Fortunately, Aniston was able to calm her down by assuring her that it was OK if she messed up. "Don't try to be perfect," Aniston advised. "Just be yourself."

They became fast friends.

"There are not that many people actually who have this incredible combination of sex appeal and complete lovability," Witherspoon said. "You just want to get your nails done with her and you want to make out with her—at least I do.

"And that's what we do sometimes on Saturdays. First we get our nails done—so cute!—and then we make out. It's totally awesome."